CN117074488B - Ultramicro electrode for high-temperature molten salt system test and preparation method and application thereof - Google Patents
Ultramicro electrode for high-temperature molten salt system test and preparation method and application thereof Download PDFInfo
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- CN117074488B CN117074488B CN202311341511.5A CN202311341511A CN117074488B CN 117074488 B CN117074488 B CN 117074488B CN 202311341511 A CN202311341511 A CN 202311341511A CN 117074488 B CN117074488 B CN 117074488B
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- 150000003839 salts Chemical class 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000010998 test method Methods 0.000 title description 2
- 229910052751 metal Inorganic materials 0.000 claims abstract description 47
- 239000002184 metal Substances 0.000 claims abstract description 47
- 238000012360 testing method Methods 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000005498 polishing Methods 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 41
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 28
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000010453 quartz Substances 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 14
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 12
- 239000004917 carbon fiber Substances 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 10
- 239000003292 glue Substances 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 5
- 239000005388 borosilicate glass Substances 0.000 claims description 3
- 229910003460 diamond Inorganic materials 0.000 claims description 3
- 239000010432 diamond Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 238000009792 diffusion process Methods 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 238000005868 electrolysis reaction Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 238000003487 electrochemical reaction Methods 0.000 abstract description 4
- 230000001052 transient effect Effects 0.000 abstract description 4
- 244000137852 Petrea volubilis Species 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000007517 polishing process Methods 0.000 abstract description 3
- 238000011056 performance test Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 37
- 238000002484 cyclic voltammetry Methods 0.000 description 13
- 229910052741 iridium Inorganic materials 0.000 description 8
- 239000003115 supporting electrolyte Substances 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 3
- 229910016655 EuF 3 Inorganic materials 0.000 description 2
- 229910013618 LiCl—KCl Inorganic materials 0.000 description 2
- 238000000563 Verneuil process Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 229940021013 electrolyte solution Drugs 0.000 description 1
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Inorganic materials [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
- C03C27/02—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing by fusing glass directly to metal
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Molecular Biology (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
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- Electrochemistry (AREA)
- Geochemistry & Mineralogy (AREA)
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Abstract
The invention belongs to the technical field of material performance test, and particularly relates to an ultramicro electrode for testing a high-temperature molten salt system, a preparation method and application thereof, wherein the preparation cost is low, the operation is simple and convenient, the yield is high, and the performance is good; compared with the metal electrode tip obtained by the traditional means, the conical metal tip obtained by the electrolysis means is more uniform, and the surface of the polished electrode is smooth and flat; the size of the conical electrode can be controlled by controlling the electrolysis time and the concentration of the strong alkali solution; the cross section size of the electrode can be controlled by changing the number of sand paper and adjusting the polishing rate in the polishing process, the prepared ultra-micro electrode has excellent usability, stability and service life in a molten salt system, and the application range is wider than that of the ultra-micro electrode in the prior art; by means of the characteristics of the ultramicro electrode, rapid and transient electrochemical reaction in a reaction system can be observed, and the method has an important effect on exploring the reaction mechanism of the whole process and measuring the low-concentration molten salt and the diffusion coefficient.
Description
Technical Field
The invention relates to the technical field of material performance testing, in particular to an ultramicro electrode for testing a high-temperature molten salt system, a preparation method and application thereof.
Background
Compared with the conventional large electrode, the ultra-micro electrode with the size smaller than 25 mu m has unique and excellent electrochemical characteristics, and the material on the ultra-micro electrode has extremely high diffusion speed due to the difference of the two material transmission modes, so that the material transmission rapidly enters a steady state or a quasi-steady state, and the cyclic voltammetry curve of the ultra-micro electrode shows an S shape; the inherently small RC time constant makes it useful for studying rapid, transient electrochemical reactions; the lower IR drop makes it possible to use in high resistance systems (including low supported electrolyte concentrations, unsupported electrolyte solutions and even gas phase systems); the smaller electrode size can not change or destroy the reaction system, and is suitable for biological living body research. Therefore, the ultra-microelectrode has wide application range in the field of electrochemical analysis. However, the existing ultramicroelectrode cannot be well used for a high-temperature molten salt system due to insufficient stability and short service life, and cannot realize detection of the high-temperature molten salt system.
Disclosure of Invention
In order to solve the problems in the prior art, the main purpose of the invention is to provide an ultramicro electrode for testing a high-temperature molten salt system, and a preparation method and application thereof.
In order to solve the technical problems, according to one aspect of the present invention, the following technical solutions are provided:
a preparation method of an ultramicro electrode for testing a high-temperature molten salt system comprises the following steps:
s1, taking a wire electrode with a certain length;
s2, placing the wire electrode at one end of an insulating high temperature resistant pipe, sealing the wire electrode at one end of the insulating high temperature resistant pipe by adopting a flame melting method, and polishing the insulating high temperature resistant pipe until the wire electrode is exposed and polished to obtain a polished wire electrode;
and S3, filling graphite powder into the insulating high temperature resistant tube, compacting the graphite powder by using a conductive metal wire, inserting the graphite powder into the graphite powder, forming an electric connection structure of a wire electrode, the graphite powder and the conductive metal wire in the insulating high temperature resistant tube, and plugging the other end of the insulating high temperature resistant tube by using high temperature glue to obtain the ultra-microelectrode.
As a preferable scheme of the preparation method of the ultra-micro electrode for testing the high-temperature molten salt system, the invention comprises the following steps: the step S3 further includes: and S4, placing the obtained ultra-microelectrode in an aqueous solution to test the stability of the ultra-microelectrode, and verifying whether the size of the wire electrode in the ultra-microelectrode is consistent with the observation result of the polished wire electrode size in the step S2 through calculation.
As a preferable scheme of the preparation method of the ultra-micro electrode for testing the high-temperature molten salt system, the invention comprises the following steps: in the step S1, the wire electrode is a metal electrode or a carbon electrode; the metal electrode comprises a platinum wire, an iridium wire and a rhodium wire, and the carbon electrode comprises graphite, carbon fiber and diamond.
As a preferable scheme of the preparation method of the ultra-micro electrode for testing the high-temperature molten salt system, the invention comprises the following steps: in the step S1, the length of the wire electrode is 2-6 cm, and the diameter of the cross section is 80-150 mu m.
As a preferable scheme of the preparation method of the ultra-micro electrode for testing the high-temperature molten salt system, the invention comprises the following steps: in the step S2, when the wire electrode is a metal electrode, the wire electrode is electrically connected to one end of the conductive metal to serve as a standby electrode, a strong alkali solution is prepared, the standby electrode is immersed in the strong alkali solution to serve as a working electrode, a metal platinum sheet is used as a counter electrode to construct an electrolytic cell system, and anode electrochemical dissolution is carried out on the wire electrode on the standby electrode to obtain a conical electrode with the cross section diameter of 5-40 mu m; and (3) placing the tip of the conical electrode outwards at one end of the insulating high-temperature-resistant pipe, sealing the tip of the conical electrode at one end of the insulating high-temperature-resistant pipe by adopting a flame fusion method, and polishing the insulating high-temperature-resistant pipe until the tip of the conical electrode is exposed and polished to obtain the polished wire electrode.
As a preferable scheme of the preparation method of the ultra-micro electrode for testing the high-temperature molten salt system, the invention comprises the following steps: in the step S2, the strong alkali solution is a NaOH solution or a KOH solution, and the concentration of the strong alkali solution is 1-10wt%; the conductive metal includes tungsten, molybdenum, nickel, and platinum.
As a preferable scheme of the preparation method of the ultra-micro electrode for testing the high-temperature molten salt system, the invention comprises the following steps: in the step S2, the insulating high temperature resistant tube is a quartz tube or a high borosilicate glass tube, the inner diameter of the insulating high temperature resistant tube is 2-6 mm, and after the wire electrode is sealed at one end of the insulating high temperature resistant tube by adopting a flame melting method, a section of wire electrode is exposed in the insulating high temperature resistant tube.
As a preferable scheme of the preparation method of the ultra-micro electrode for testing the high-temperature molten salt system, the invention comprises the following steps: in the step S3, the conductive metal wire comprises a tungsten wire, a molybdenum wire, a nickel wire and a platinum wire, and the diameter of the cross section of the conductive metal wire is 1-4 mm.
As a preferable scheme of the preparation method of the ultra-micro electrode for testing the high-temperature molten salt system, the invention comprises the following steps: in the step S3, the exposed wire electrode is required to be completely covered by the graphite powder, the graphite powder column is compact and tight as much as possible, and the conductive metal wire extends out of one end of the insulating high-temperature-resistant tube, which is plugged by high-temperature glue, for 5-15 cm.
As a preferable scheme of the preparation method of the ultra-micro electrode for testing the high-temperature molten salt system, the invention comprises the following steps: in the step S4, the aqueous solution is K of 1-30 mM 3 Fe(CN) 6 The solution (supporting electrolyte is 1mol/L KCl solution), the cyclic voltammogram is measured, the scanning range is 0-0.45V, and the scanning speed is 10mV/s.
In order to solve the above technical problems, according to another aspect of the present invention, the following technical solutions are provided:
the ultra-micro electrode for testing the high-temperature molten salt system is prepared by adopting the preparation method.
In order to solve the above technical problems, according to another aspect of the present invention, the following technical solutions are provided:
the application of the ultramicro electrode for testing the high-temperature molten salt system in the high-temperature molten salt system test is provided.
The beneficial effects of the invention are as follows:
the invention provides an ultramicro electrode for testing a high-temperature molten salt system, and a preparation method and application thereof, wherein the preparation cost is low, the operation is simple and convenient, the yield is high, and the performance is good; compared with the metal electrode tip obtained by the traditional means, the conical metal tip obtained by the electrolysis means is more uniform, and the surface of the polished electrode is smooth and flat; the size of the conical electrode can be controlled by controlling the electrolysis time and the concentration of the strong alkali solution; the cross section size of the electrode can be controlled by changing the number of sand paper and adjusting the polishing rate in the polishing process, the prepared ultra-micro electrode has excellent usability, stability and service life in a high-temperature molten salt system, and the application range is wider than that of the ultra-micro electrode in the prior art; by means of the characteristics of the ultramicro electrode, rapid and transient electrochemical reaction in a reaction system can be observed, and the method has an important effect on exploring the reaction mechanism of the whole process and measuring the low-concentration molten salt and the diffusion coefficient.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to the structures shown in these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an optical microscope view of a polished wire electrode of the present invention.
FIG. 2 shows K at 30 mM for the ultra-microelectrode prepared according to example 1 of the present invention 3 Fe(CN) 6 Cyclic voltammogram at a scan rate of 10mV/s in solution (1 mol/L KCl solution for supporting electrolyte).
FIG. 3 shows K of 30 mM of the ultra-micro electrode prepared in example 2 of the present invention 3 Fe(CN) 6 Cyclic voltammogram at a scan rate of 5mV/s in solution (1 mol/L KCl solution for supporting electrolyte).
FIG. 4 shows the LiCl-KCl blank salt+SmCl of the ultra-micro electrode prepared in example 1 of the present invention 3 The system was scanned at a cyclic voltammogram of 10mV/s.
FIG. 5 shows the result of example 2 of the present invention in LiF-NaF-KF blank salt+EuF 3 Scanning speed in systemCyclic voltammogram with a degree of 10mV/s.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
The following description will be made clearly and fully with reference to the technical solutions in the embodiments, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides an ultramicro electrode for testing a high-temperature molten salt system, a preparation method and application thereof, and the prepared ultramicro electrode has excellent usability, stability and service life in the high-temperature molten salt system, and has wider application range compared with the ultramicro electrode in the prior art. The high temperature molten salt system comprises a chloride system, a carbonate system and a fluoride system (such as LiCl base, caCl 2 Radical, li 2 CO 3 The working temperature of the base and LiF-NaF-KF system is 400-900 ℃.
According to one aspect of the invention, the invention provides the following technical scheme:
a preparation method of an ultramicro electrode for testing a high-temperature molten salt system comprises the following steps:
s1, taking a wire electrode with a certain length;
s2, placing the wire electrode at one end of an insulating high temperature resistant pipe, sealing the wire electrode at one end of the insulating high temperature resistant pipe by adopting a flame melting method, and polishing the insulating high temperature resistant pipe until the wire electrode is exposed and polished to obtain a polished wire electrode;
s3, filling graphite powder into the insulating high temperature resistant pipe from the end, which is not sealed, of the insulating high temperature resistant pipe, compacting the graphite powder by using a conductive metal wire, inserting the graphite powder into the graphite powder, forming an electric connection structure of a wire electrode, the graphite powder and the conductive metal wire in the insulating high temperature resistant pipe, and sealing the other end of the insulating high temperature resistant pipe by using high temperature glue to obtain the ultra-micro electrode.
Preferably, the step S3 further includes: and S4, placing the obtained ultra-microelectrode in an aqueous solution to test the stability of the ultra-microelectrode, and verifying whether the size of the wire electrode in the ultra-microelectrode is consistent with the observation result of the polished wire electrode size in the step S2 (the optical microscope observation diagram is shown in figure 1) through calculation. The cross section of the standard metal wire electrode is circular, but the standard metal wire electrode is deformed after sintering preparation, and the electrode area can be estimated through electrochemical tests to judge whether the standard metal wire electrode is consistent with the observed electrode area.
Preferably, in the step S1, the length of the wire electrode is 2-6 cm, and the diameter of the cross section is 80-150 μm. The wire electrode is a metal electrode or a carbon electrode; the metal electrode comprises a platinum wire, an iridium wire and a rhodium wire, and the carbon electrode comprises graphite, carbon fiber and diamond. Specifically, the length of the wire electrode may be, for example, but not limited to, a range between any one or any two of 2cm, 3cm, 4cm, 5cm, 6cm, and the cross-sectional diameter may be, for example, but not limited to, a range between any one or any two of 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm.
Preferably, in the step S2, when the wire electrode is a metal electrode, the wire electrode is electrically connected to one end of the conductive metal to serve as a standby electrode, a strong alkali solution is prepared, the standby electrode is immersed in the strong alkali solution to serve as a working electrode, a metal platinum sheet is used as a counter electrode to construct an electrolytic cell system, and anode electrochemical dissolution is performed on the wire electrode on the standby electrode to obtain a conical electrode; and (3) placing the tip of the conical electrode outwards at one end of the insulating high temperature resistant pipe, sealing the tip of the conical electrode at one end of the insulating high temperature resistant pipe by adopting a flame melting method, and polishing the insulating high temperature resistant pipe until the tip of the conical electrode is exposed and polished to obtain the conical electrode with the cross section diameter of 5-40 mu m. Further preferred, the conductive metal comprises tungsten, molybdenum, nickel, platinum. The diameter of the cross section of the conductive metal is 1.5-2.5 mm, and the extension length of the wire electrode after the wire electrode is electrically connected to one end of the conductive metal is 1.5-5.5 cm.
Preferably, in the step S2, the strong alkali solution is NaOH solution or KOH solution, and the concentration thereof is 1-10wt%. Specifically, the concentration of the strong base solution may be, for example, but not limited to, any one of 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt% or a range between any two.
Preferably, in the step S3, the insulating high temperature resistant tube is a quartz tube or a borosilicate glass tube, the inner diameter of the insulating high temperature resistant tube is 2-6 mm, and after the wire electrode is sealed at one end of the insulating high temperature resistant tube by adopting a flame melting method, a section of the wire electrode is exposed in the insulating high temperature resistant tube. In particular, the inner diameter of the insulating refractory tube may be, for example, but not limited to, any one or a range between any two of 2mm, 3mm, 4mm, 5mm, 6 mm.
Preferably, in the step S4, the conductive metal wire includes a tungsten wire, a molybdenum wire, a nickel wire, and a platinum wire, and the diameter of the cross section of the conductive metal wire is 1-4 mm. The graphite powder is required to completely cover the exposed wire electrode in the insulating high-temperature-resistant tube, the graphite powder column is compact and solid as much as possible, and the conductive metal wire extends out of one end of the insulating high-temperature-resistant tube, which is plugged by high-temperature glue, for 5-15 cm. In particular, the cross-sectional diameter of the conductive wire may be, for example, but not limited to, any one or a range between any two of 1mm, 2mm, 3mm, 4 mm; the length of the conductive wire extending from one end of the insulating refractory tube plugged with the high temperature glue may be, for example, but not limited to, any one or a range between any two of 5cm, 6cm, 7cm, 8cm, 9cm, 10cm, 11cm, 12cm, 13cm, 14cm, 15cm.
Preferably, in the step S5, the aqueous solution is 1-30 mM K 3 Fe(CN) 6 The solution (supporting electrolyte is 1mol/L KCl solution), the cyclic voltammogram is measured, the scanning range is 0-0.45V, and the scanning speed is 10mV/s.
Preferably, in the step S5, according to the measured data in the aqueous solution, an ultramicro electrode steady-state current calculation formula is combined:wherein->Is steady-state current, n is the number of electrons transferred by electrode reaction, F is Faraday constant, D is the diffusion coefficient of reactive ions, ">For the concentration of reactive ions>Cross-sectional radius of wire electrode in the microelectrode. The actual size of the wire electrode in the ultramicroelectrode is obtained through calculation and compared with the observation result of the optical microscope, and whether the calculation result is consistent with the observation result is verified.
According to another aspect of the invention, the invention provides the following technical scheme:
the ultra-micro electrode for testing the high-temperature molten salt system is prepared by adopting the preparation method.
The application of the ultramicro electrode for testing the high-temperature molten salt system in the high-temperature molten salt system test is provided.
The ultramicroelectrode for testing the high-temperature molten salt system is used for testing the electrode reaction mechanism in the high-temperature molten salt system and measuring the low-concentration molten salt or diffusion coefficient. For example, according to the steady-state current calculation formula of the microelectrode:knowing the system concentration, and calculating the material diffusion coefficient at a certain temperature according to the measurement result; knowing the diffusion coefficient of the substance at this temperature, the concentration of the substance to be detected can be calculated from the steady-state current.
The technical scheme of the invention is further described below by combining specific embodiments.
Example 1
A preparation method of an ultramicro electrode for testing a high-temperature molten salt system comprises the following steps:
s1, taking iridium wires with the length of 2.5cm and the cross section diameter of 120 mu m;
s2, respectively and electrically connecting the iridium wires with the extension length of 2cm to one end of a nickel rod with the cross section diameter of 2mm to serve as a standby electrode; preparing an NaOH solution with the concentration of 5wt%, immersing a standby electrode in the NaOH solution to serve as a working electrode, constructing an electrolytic cell system by taking a metal platinum sheet as a counter electrode, and carrying out anode electrochemical dissolution on iridium on the standby electrode for 20min to obtain conical iridium with the cross section diameter ranging from 10 mu m to 15 mu m; the method comprises the steps of (1) placing the tip of a conical iridium wire outwards at one end of a quartz tube with the inner diameter of 2mm and the length of 20cm, sealing the tip of the conical iridium wire at one end of the quartz tube by adopting a flame melting method, exposing a small section of iridium wire in the tube for electric connection, polishing the quartz tube until the tip of the conical iridium wire is exposed and polished to obtain polished iridium wire; observing the cross section of the iridium wire by using an optical microscope, and obtaining the cross section size of the iridium wire with the aid of an eyepiece micrometer, wherein the diameter is about 12 mu m;
and S3, filling graphite powder into the quartz tube, compacting the graphite powder by using a tungsten wire with the cross section diameter of 1mm and the length of 25cm, polishing the tungsten wire to be smooth, then inserting the tungsten wire into the graphite powder, forming an electric connection structure of the micron iridium wire, the graphite powder and the tungsten wire in the tube, and plugging the other end of the quartz tube by using high-temperature glue to obtain the ultramicro electrode.
The resulting microelectrode of this example was placed in a K of 30 mM 3 Fe(CN) 6 The solution (supporting electrolyte is 1mol/L KCl solution), and the cyclic voltammogram (shown in FIG. 2) is measured, the scanning range is 0-0.45V, and the scanning speed is 10mV/s. By the formulaCalculating to obtain the radius r of the cross section of the iridium wire in the ultra-micro electrode 1 =5.98 μm, substantially consistent with observations.
The ultra-microelectrodes obtained in this example were rinsed and dried to prepare 13.4. 13.4 mM SmCl in LiCl-KCl blank salt 3 The salt was subjected to cyclic voltammetry at a sweep rate of 10mV/s and the results are shown in FIG. 4. Known SmCl 3 Concentration, measurement of SmCl at the same temperature 3 Diffusion coefficient D of (a).
Example 2
A preparation method of an ultramicro electrode for testing a high-temperature molten salt system comprises the following steps:
s1, taking iridium wires with the length of 2.5cm and the cross section diameter of 120 mu m;
s2, respectively and electrically connecting the iridium wires with the extension length of 2cm to one end of a nickel rod with the cross section diameter of 2mm to serve as a standby electrode; preparing an NaOH solution with the concentration of 5wt%, immersing a standby electrode in the NaOH solution to serve as a working electrode, constructing an electrolytic cell system by taking a metal platinum sheet as a counter electrode, and carrying out anode electrochemical dissolution on iridium on the standby electrode for 6min to obtain conical iridium with the cross section diameter ranging from 35 mu m to 40 mu m; the method comprises the steps of (1) placing the tip of a conical iridium wire outwards at one end of a quartz tube with the inner diameter of 2mm and the length of 20cm, sealing the tip of the conical iridium wire at one end of the quartz tube by adopting a flame melting method, exposing a small section of iridium wire in the tube for electric connection, polishing the quartz tube until the tip of the conical iridium wire is exposed and polished to obtain polished iridium wire; observing the cross section by using an optical microscope, and obtaining the cross section size of the polished iridium wire with the aid of an eyepiece micrometer, wherein the diameter is 37.6 mu m;
and S3, filling graphite powder into the quartz tube, compacting the graphite powder by using a tungsten wire with the cross section diameter of 1mm and the length of 25cm, polishing the tungsten wire to be smooth, then inserting the tungsten wire into the graphite powder, forming an electric connection structure of the micron iridium wire, the graphite powder and the tungsten wire in the tube, and plugging the other end of the quartz tube by using high-temperature glue to obtain the ultramicro electrode.
The resulting microelectrode of this example was placed in a K of 30 mM 3 Fe(CN) 6 The solution (supporting electrolyte is 1mol/L KCl solution), and the cyclic voltammogram (shown in FIG. 3) is measured, the scanning range is 0-0.45V, and the scanning speed is 5mV/s. By the formulaCalculating to obtain the radius r of the cross section of the iridium wire in the ultra-micro electrode 2 =18.92 μm, substantially consistent with observations.
Preparing LiF-NaF-KF blank salt and low-concentration EuF 3 Molten salt, euF at 600 ℃ is known to obtain cyclic voltammogram of the ultramicroelectrode test system by using the embodiment 3 Diffusion coefficient d=10.7×10 -10 m 2 s -1 The cyclic voltammogram was measured from the microelectrode and the results are shown in FIG. 5. According to the steady-state current calculation formula of the ultramicroelectrodeKnowing the electrode size, the EuF in the system can be determined 3 The concentration is checked by comparing the measured concentration with the configured concentrationThe accuracy of detection is proved, and the method is popularized to other molten salt systems.
Example 3
A preparation method of an ultramicro electrode for testing a high-temperature molten salt system comprises the following steps:
s1, taking carbon fiber with the length of 2cm and the cross section diameter of 9 mu m;
s2, placing the carbon fiber at one end of a quartz tube with the inner diameter of 2mm and the length of 20cm, sealing the carbon fiber at one end of the quartz tube by adopting a flame fusion method, exposing a small section of carbon fiber in the tube for electric connection, and polishing the quartz tube until the carbon fiber is exposed and polished to obtain polished carbon fiber; observing the cross section by using an optical microscope, and obtaining the cross section size of the polished carbon fiber with the aid of an eyepiece micrometer, wherein the diameter is about 9 mu m;
and S3, filling graphite powder into the quartz tube, compacting the graphite powder by using molybdenum wires with the cross section diameter of 1mm and the length of 25cm, polishing the molybdenum wires to be smooth, then inserting the molybdenum wires into the graphite powder, forming an electric connection structure of carbon fiber, graphite powder and molybdenum wires in the tube, and plugging the other end of the quartz tube by using high-temperature glue to obtain the ultramicro electrode.
Placing the obtained ultramicroelectrode at K of 15 mM 3 Fe(CN) 6 The solution (supporting electrolyte is 1mol/L KCl solution), the cyclic voltammogram is measured, the scanning range is 0-0.45V, and the scanning speed is 10mV/s. By the formulaThe diameter of the cross section of the carbon fiber in the ultramicroelectrode is 9 μm, which is basically consistent with the observation result.
Washing and drying the obtained ultramicroelectrode, and adding LiF-LiCl-LiBr blank salt and Li 2 CO 3 The system is subjected to cyclic voltammetry, and the reaction mechanism is explored.
The invention has low preparation cost, simple operation, high yield and good performance; compared with the metal electrode tip obtained by the traditional means, the conical metal tip obtained by the electrolysis means is more uniform, and the surface of the polished electrode is smooth and flat; the size of the conical electrode can be controlled by controlling the electrolysis time and the concentration of the strong alkali solution; the cross section size of the electrode can be controlled by changing the number of sand paper and adjusting the polishing rate in the polishing process, the prepared ultra-micro electrode has excellent usability, stability and service life in a high-temperature molten salt system, and the application range is wider than that of the ultra-micro electrode in the prior art; by means of the characteristics of the ultramicro electrode, rapid and transient electrochemical reaction in a reaction system can be observed, and the method has an important effect on exploring the reaction mechanism of the whole process and measuring the low-concentration molten salt and the diffusion coefficient.
The foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the invention, and all equivalent structural changes made by the content of the present invention or direct/indirect application in other related technical fields are included in the scope of the present invention.
Claims (7)
1. The preparation method of the ultramicro electrode for testing the high-temperature molten salt system is characterized by comprising the following steps of:
s1, taking a wire electrode with a certain length; the wire electrode is a metal electrode or a carbon electrode, the metal electrode is a platinum wire, an iridium wire or a rhodium wire, and the carbon electrode is graphite, carbon fiber or diamond; the diameter of the cross section of the metal electrode is 80-150 mu m;
s2, placing the wire electrode at one end of an insulating high temperature resistant pipe, sealing the wire electrode at one end of the insulating high temperature resistant pipe by adopting a flame melting method, and polishing the insulating high temperature resistant pipe until the wire electrode is exposed and polished to obtain a polished wire electrode; when the wire electrode is a metal electrode, electrically connecting the wire electrode to one end of the conductive metal to serve as a standby electrode, preparing a strong alkali solution, immersing the standby electrode in the strong alkali solution to serve as a working electrode, constructing an electrolytic cell system by taking a metal platinum sheet as a counter electrode, and performing anodic electrochemical dissolution on the wire electrode on the standby electrode to obtain a conical electrode with the cross section diameter of 5-40 mu m; the tip of the conical electrode is outwards arranged at one end of an insulating high temperature resistant pipe, the tip of the conical electrode is sealed at one end of the insulating high temperature resistant pipe by adopting a flame melting method, and then the insulating high temperature resistant pipe is polished until the tip of the conical electrode is exposed and polished, so that a polished wire electrode is obtained;
in the step S2, the insulating high temperature resistant tube is a quartz tube or a high borosilicate glass tube, the inner diameter of the insulating high temperature resistant tube is 2-6 mm, and after the wire electrode is sealed at one end of the insulating high temperature resistant tube by adopting a flame melting method, a section of wire electrode is exposed in the insulating high temperature resistant tube;
and S3, filling graphite powder into the insulating high temperature resistant tube, compacting the graphite powder by using a conductive metal wire, inserting the graphite powder into the graphite powder, forming an electric connection structure of a wire electrode, the graphite powder and the conductive metal wire in the insulating high temperature resistant tube, and plugging the other end of the insulating high temperature resistant tube by using high temperature glue to obtain the ultra-microelectrode.
2. The method for preparing the ultra-micro electrode for the high-temperature molten salt system test according to claim 1, wherein in the step S1, the length of the wire electrode is 2-6 cm.
3. The method for preparing the ultra-microelectrode for the high-temperature molten salt system test according to claim 1, wherein in the step S2, the strong alkali solution is a NaOH solution or a KOH solution, and the concentration thereof is 1-10wt%; the conductive metal includes tungsten, molybdenum, nickel, and platinum.
4. The method for preparing the ultra-microelectrode for the high-temperature molten salt system test according to claim 1, wherein in the step S3, the conductive metal wire comprises tungsten wire, molybdenum wire, nickel wire and platinum wire, and the diameter of the cross section of the conductive metal wire is 1-4 mm.
5. The method for preparing the ultra-microelectrode for the high-temperature molten salt system test according to claim 1, wherein in the step S3, the exposed wire electrode is required to be completely covered by the graphite powder, and the conductive metal wire extends out of one end of the insulating high-temperature resistant tube, which is plugged by high-temperature glue, by 5-15 cm.
6. An ultramicro electrode for high temperature molten salt system test, prepared by the preparation method of any one of claims 1-5.
7. Use of the ultra-microelectrode for high-temperature molten salt system testing according to claim 6 in high-temperature molten salt system testing.
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